Process for preparing vicinal glycols from olefins

ABSTRACT

Process for preparing haloesters, halohydrins and vicinal glycols by halogenating olefins in the presence of water and an amide.

United States Patent mi Heckert et al.

[451 Oct. 9, 1973 PROCESS FOR PREPARING VICINAL GLYCOLS FROM'OLEF INSInventors: David C. Heckert, Oxford; Donald V. Julian, ColerainTownship, Hamilton County, both of Ohio The Procter & Gamble Company,Cincinnati, Ohio Filed: June '29, 1970 Appl No.: 51,022

Assignee:

Int. Cl... C07c 29/02, C07c 31/34, C070 67/00 Field of Search 260/635 H,410.9 R,

[56] References Cited UNITED STATES PATENTS 3,427,347 2/1969 Lapporte260/491 3,562,315 2/1971 Cookson et al 250/493 FOREIGN PATENTS ORAPPLICATIONS 529,476 11/1940 Great Britain Primary Examiner-Lewis GottsI Assistant Examiner-Diana G. Rivers Attorney-Jack D. Schaeffer andRichard C. Wine ABSTRACT Process for preparing haloesters, halohydrinsand vici- -nalglycols by halogenating olefins in the presence of waterand an amide.

7 Claims, No Drawings PROCESS FOR PREPARING VICINAL GLYCOLS FROM OLEFINSBACKGROUND OF THE INVENTION This invention relates to an improvedprocess for the preparation of haloesters, halohydrins and vicinalglycols by the reaction of halogens with olefins.

It is well recognized that the halogenation of olefins generallyproceeds almost exclusively by addition across the olefinic double bondand results in the formation of vicinal dihalides. To effect the vicinalhalogenation of olefins all that is required is that the halogen beadded in the requisite amount to the olefin. In the case of chlorine,this is conveniently accomplished by bubbling the halogen through theolefin or a solution thereof. Bromine and iodine may be convenientlyadded portionwise to the olefin and allowed to react. Often, a competingreaction is replacement of hydrogen in the olefin by the halogen. Tominimize this, the reaction can be done in a solvent which serves as adiluent and thereby moderates the reaction so that simple addition ofthe halogen across the double bond is the predominant reaction whichoccurs. Alternatively, the.

halogen can be diluted. When chlorine is being employed, it isconveniently diluted with air or an inert gas. Bromine and iodine can bedissolved in a solvent and added portionwise, in dilute solution, to theolefin. Commonly, both the olefin and the halogen are so diluted priorto admixing. The halogenation reaction of the present invention differsfrom the prior art halogenation of olefins in that it occurs only in thepresence of certain amide/water mixtures hereinafter described andresults not in the formation of the expected vicinal dihalides, butrather, in reaction products containing a single halogen atom and agroup derived from the amideor in vicinal glycols or halohydrins.

Under certain of the conditions hereinafter defined, halogenation ofolefins by the process of this invention results in the formation ofvicinal haloesters. Such haloesters find use as plasticizers andintermediates in the preparation of commercially important epoxidematerials. By suitable variations in the details of the presenthalogenation reaction, halohydrins are produced. These halohydrins areuseful as plasticizers and as starting materials in the base-catalyzedpreparation of commercially important epoxides and glycols. In addition,the halogenation of olefins by the present process under the appropriateconditions results in the formation of vicinal glycols. Vicinal glycols,in turn, are important additives for polyesters and also serve asstarting materials in the preparation of carboxylic acids by the processdescribed in the co-pending application of E. P. Pultinas, Jr., Ser. No.51,023 filed June 29, 1970, now abandoned.

Accordingly, it is a primary object of the present invention to providean improved process for the preparation of haloesters, halohydrins andvicinal glycols. It is a further object of this invention to provide aquick, effective means for the conversion of olefins to haloesters,halohydrins and vicinal glycols. These and other objects and obtained bythe present invention as will become apparent from the followingdisclosure.

SUMMARY OF THE INVENTION The process of the present invention comprisesreacting an olefin with a halogen in the presence of a mixture ofcertain amides and water, in specified proportions, all as hereinafterdisclosed. The specific reaction product of the present process(halohydrin, haloester or glycol) depends primarily on the proportionofwater relative to olefin present in the reaction mixture. Reaction A,depicted below, illustrates the preparation of haloesters by thehalogenation reaction of this invention performed in the presence ofamide and one equivalent of water. Reaction B, depicted below,illustrates the preparation of halogydrins by the halogenation in thepresence of amide and two equivalents of water. Reaction C illustratesthe preparation of glycols in the presence of amide and three or moreequivalents of water.

wherein X represents halogens (preferably bromine and chlorine) otherthan fluorine and wherein each R represents hydrogen, alkyl containingfrom one to about 25 carbon atoms, aryl (e.g., phenyl, naphthyl,anthracenyl, phenylethyl, benzyl), carboxyalkyl (i.e., (CI-I )',,COOI- lwhere n is 1-25), alkoxy, alkylglycerylester, alkylester, nitroalkyl,haloalkyl, polyalkoxyalkyl, and the like. Chlorine is especiallypreferred as the halogen for economic reasons.

Olefins which can be used in the practice of the present invention arelimited only in that they must be miscible with the amide/water mixture.Olefins having from two to about 102 carbon atoms, and preferably fiveto 20 carbon atoms, are all suitable for use here. Such olefins can bederived from any of a number of well-known sources. For example, olefinsdistilled from petroleum feedstocks are suitably employed in thepractice of the present invention. Similarly, alkenes formed fromrefinery gases resulting from the industrial cracking of petroleum canbe used as well as olefins formed by the partial hydrogenation of acetylenic hydrocarbons.

Cyclic olefins having from about four to about 20- carbon atoms andpreferably from about five to about 12 carbon atoms are also suitablefor use herein.

Non-limiting examples of olefins which can be halogenated in accordancewith this invention include cyclopentene, cyclohexene, cyclooctene,cyclododecene, cyclo-eicosene, l-pentene, 2-pentene, l-hexene, 2-hexene, 3-h'exene, l-heptene, Z-heptene, 3-heptene, loctene, 2-octene,l-nonene, 2-nonene, 3-nonene, 4-

nonene, l-decene, l-undecene, l-dodecene, 2- dodecene, 3-dodecene,4-dodecene, 5-dodecene, ltridecene, l-tetradecene, l-pentadecene,l-hexcosene, 2-hexcosene, 3-docosene, l-octadecene and 1- heneicosene.The novel reaction of the present invention proceeds well with bothterminal and internal olefins.

Exemplary branched-chain olefins suitable for use in the novel reactionof this invention include 2-methyl-lpentene, 2-naphthyl-3-hexene and2-phenyl-4- dodecene, all of which form the reaction productscorresponding to Reaction A, B or C, as outlined in the general reactionscheme, depending on whether one, two or three equivalents of water,based on olefin, are present with the amide.

Various unsaturated fatty acids and their esters, especially thoseobtainable from natural fats and waxes, can be halogenated in thepresent process. For example, oleic acid, ricinoleic acid, palmitoleicacid, petroselinic acid, vaccenic acid, erucic acid and the like, can bereacted with halogen in the presence of amide and water according to thepresent process and, depending upon the mole equivalents of waterpresent as hereinbefore described, undergo either a type A, B or Creaction and result in the corresponding products as detailed in theworking examples hereinafter provided.

Commercially available mixtures of fatty acids and their alkyl estersobtainable from, a wide variety of natural animal and plant fats andwaxes can also be halogenated in the practice of the present invention.Such mixtures contain both unsaturated and saturated fatty acids. Thesaturated fatty acids are not involved in the reaction by virtue oftheir lack of olefinic linkages; they are present in the reactionmixtures as mere diluents and can be removed at a convenient time sothat the.

desired reaction products can be isolated. Any of the common sources offatty acid mixtures can be used to provide suitable fatty acids. Palmoil, peanut oil, corn oil, linseed oil, soybean oil, lard, tallow,Neats-foot oil and the like, are all suitable sources for glycerideswhich, upon hydrolysis, yield acid mixtures suitable for halogenation.

Alternatively, those glycerides containing unsaturated fatty acids whichare present in the various natural fats and oils can be directly reactedwith halogen in the presence of the amide/water mixture without priorhydrolysis to yield the haloester, halohydrin or glycol derivatives ofthe respective glycerides. For example, in this fashion thecorresponding haloesters, halohydrins and glycols of palm oil, peanutoil, corn oil, linseed oil, tallow, lard, soybean oil, babassu oil,Neats-foot oil, whale oil and the like are prepared using thehalogenation process herein disclosed.

Especially preferred olefinic compounds used in the practice of thisinvention are l-octene, l-decene, ldodecene, l-tetradecene,l-hexadecene, l-octadecene, oleic acid, methyl oleate, ricinoleic acid,and methyl ricinoleate. The unsaturated glyceride esters hereinbeforenoted are also preferred olefinic compounds used in the practice of thisinvention. Of these glyceride es; ters, those present in lard, tallowand soybean oil are especially preferred.

dimethylbenzamide,

The amides suitable for use in the present process are those which donot contain a nitrogen-hydrogen (N-H) bond; that is to say, dialkyl,diaryl, and alkylaryl amides. Likewise, both water and the olefinundergoing reaction must be suitably co-miscible with such amides.Amides having the general formula R'C(O)NR"R"', wherein R is a memberselected from the group consisting of hydrogen, normal, branched-chainand cyclic alkyl groups containing from'about one to about 10carbonatoms, preferably from about one to about seven carbon atoms,andphenyl and wherein R" and R' are each members selected from the groupconsisting of normal, branchedchain, and cyclic alkyl groups containingfrom about one to about 10 carbon atoms, preferably from about one toabout five carbon atoms and phenyl, are suitable for use. If it isdesired to perform the reaction of the present invention at roomtemperatures, amides having low molecular weights can be used since theyare liquids at such temperatures. Should it be desired to do thereaction at higher temperatures, either the lower alkyl amides or thealkyl amides having the longer chains in the above-recited ranges can beutilized in that these latter compounds will be liquified at suchtemperatures.

Non-limiting examples of amides suitable for use as the solvent in thepractice of the novel process of this invention include:dimethylformamide, diethylformamide, dipropylformamide,dibutylformamide, dioctylformamide, didecylformamide, dimethylacetamide,dimethylpropionamide, dimethylbutyramide, dimethylpentanamide,dimethylcyclohexanamide, dimethyldecanamide, diethylacetamide,dipropylpropanamide, dibutylbutyramide, dicyclopentylbutyramide,dioctyldecanamide, didecyldecanamide, diphenylacetamide,

methylphenylacetamide, diphenylbenzamide and dimethylcyclohexanamide.Any of these amides can be prepared by the condensation of thecorresponding acid or acid halide with the corresponding dialkyl ordiaryl amine in the manner wellknown to those skilled in the art.Certain tetraalkyl diamides can be suitably employed in the practice ofthe novel process of this invention. For example, N,N,N',N- tetraalkyldiamides of oxalic acid, malonic acid, succinic acid, etc., wherein thealkyl groups are those hereinbefore noted as suitable for use in themono-amide materials utilized in the novel process of the presentinvention, may be suitably employed. Preferred amides useful in thepractice of the present invention are the N,N-dimethylakanoyl amides.Especially preferred amides suitable for use in the practice of thepresent invention are: dimethylformamide, dimethylacetamide,dimethylpropionamide, dimethylbutyramide, dimethylpentanamide,dimethyloctanamide, dimethylnonanamide, dimethyldecanamide anddimethylbenzamide.

According to the general reaction scheme, Reaction A involves thehalogenation of an olefin in the presence of an amide and one equivalentof water for each equivalent of olefin present in the reaction mixture.To achieve optimum yields of haloester, at least two moles of amide foreach mole of olefin should be present since one mole of amide isconsumed in the formation of amide hydrohalide by-product. (This is alsotrue in B and C.) However, the process does occur as indicated inReaction A if less amide is used, albeit in reduced product yields. Thereaction product is a haloester whose ester functionality is derivedfrom the alkanoyl group of the amide. For example, halogenation of anolefin in the presence of one equivalent of water and two equivalents ofdimethylformamide according to the process of this invention results inthe formation of the haloformate ester of the parent olefin. Likewise,use of dimethylacetamide results in the formation of the haloacetateester of the parent olefin. Likewise, use of dimethylpropionamideresults in the formation of the halopropionate ester of the parentolefin. Thus haloesters having nearly any desired ester functionalitycan be prepared by the process of this invention as represented byReaction A by using an amide which has the desired alkanoyl group. Ofcourse, the halogen functionality can similarly be varied by the choiceof halogen used as hereinbefore described.

Reaction A is most preferably performed by mixing the selected olefinand about a five-fold to 20-fold molar excess of amide together with oneequivalent of water for each equivalent of olefin and adding thereto,portionwise, one equivalent of halogen. The reaction proceeds readilywithout initiation and is exothermic. The reaction products are nottemperature dependent and good yields of haloesters are formed attemperatures from 30 to 200C. and preferably from about 0C. to aboutl00C.

As hereinbefore disclosed, use of two moles of water for each equivalentof olefin results in a reaction represented herein as Reaction B. Again,for best results, two moles of amide per mole of olefin should bepresent. If less amide is used, product yields are reduced. The productof this reaction is not a haloester, but rather, a halohydrin. lnReaction B, the olefin is conveniently admixed with a five-fold to20-fold molar excess of amide and two equivalents of water perequivalent of olefin. One equivalent of halogen per equivalent of olefinis added to the reaction mixture, portionwis'e, and a halohydrin isformed.

The reaction products formed in Reaction B do not depend on temperatureand pressure and halohydrins can be prepared by this process attemperatures ranging from about 30C. to about 200C. and preferably from0 to 100C. In some instances it may be convenient to use an excess ofwater to insure completion of the reaction. If an excess of water isused with theamide, the reaction temperature must be maintained at orbelow 160C. to avoid the reaction of the halohydrins to form vicinalglycols (Reaction C). This glycol formation does not occur if the amountof water in the amide is limited to two equivalents, based on the amountof olefin used in the reaction.

Reaction C can be used if it is desired to prepare vicinal glycolsdirectly from olefins. This is conveniently done by halogenating anolefin of the type herein described in the presence of at least threemoles of water per mole of olefin in an excess of an amide, as hereindetailed, at temperatures above 160C., preferably 170 to 250C. Any ofthe olefins as hereinbefore disclosed will undergo conversion to theircorresponding vicinal glycol when so treated in the presence of at leastthree moles of water and an amide of the type noted previously. Bromine,chlorine and iodine represent halogens suitable for use in this process,with bromine and chlorine being preferred. Chlorine is especiallypreferred halogen for use in this glycol synthesis.

Reaction A, Reaction B and Reaction C are not dependent on pressure andmay be run at pressures between 1 and 1,000 atmospheres. Reaction C ispreferably done at 30-200 psi. so as to prevent water loss at thereaction temperatures.

The rates of Reactions A, B and C can be varied by the rate of halogenaddition, but the nature of the reaction products does not dependthereon. Chlorine is the preferred halogen for use in Reactions A, B andC for economic reasons. a

The following Examples, which are not intended to be limiting, serve todemonstrate the process of this invention.

REACTION A EXAMPLE 1 Reaction of l-Decene with Chlorine inDimethylformamide A mixture of 6.3 g. (0.045 mole) of l-decene, 0.8 g.(0.045 mole) of water, and 100 ml. of dry dimethylformamide (DMF) wasplaced in a 250 ml. flask equipped with a mechanical stirrer. A mixtureof chlorine and air was passed into the reaction mixture at the rate of4 meq., Cl /min. until a total of 0.045 moles of Cl, has been added. Thereaction mixture was poured into 300 ml. of water and quickly extractedwith three- 150 ml. portions od diethyl ether. The ether extracts weredried over MgSO and the ether was removed by distillation.Chromatography (Carbowax/220C./He flow ml. /min.) indicated that theproduct contained 89 percent chloroformyloxydecane (2 isomers), 9percent l,2-dichlorodecane, and a trace of the chlorohydrins (2isomers). Vacuum distillation yielded 8.3 g. (84 percent) of EXAMPLE 11Reaction of l-Decene with Chlorine in Dimethylacetamide A mixture of 6.3g. (0.045 mole) of l-decene, 0.8 g. (0.045 mole) of H 0, and ml. of drydimethylacetamide (DMAC) was placed in a 250 ml. flask and stirred. Amixture of chlorine and air was passed into the reaction mixture at therate of 4 meq. of Cl lmin. until a total of 0.045 mole of C1 had'beenadded. The reaction mixture was poured into 300 ml. H 0 and extractedwith threeml. portions of diethyl ether.

The combined ether extracts were dried over MgSO.

and the ether was removed by distillation. The remaining material wasanalyzed by gas-liquid chromatography and proved to be 90 percentchloroacetoxydecane (2 isomers), 9 percent dichloride and about 1percent chlorohydrin. Vacuum distillation yielded 9.1 g. (86 percent) ofthe chloroacetate (l)COCH C H CHCH CI (2 isomers) b.p. 78-79/ 0.05 mm.Hg.

An equivalent amount of dimethylpropionamide, diethylacetamide, anddimethylbenzamide, respectively, is substituted for thedimethylacetamide in the above process and the reaction products aremixtures of isomers of the corresponding chloroester, i.e., decanechloropropionate, decane chloroacetate, and decane chlorobenzoate,respectively.

EXAMPLE lll Chlorination of Soybean Oil in Dimethylformamide 11.68 g.soybean oil (SBO) (Approx. 0.013 M) (double bond equivalent weight 188),1.08 g. H and 135 ml. dimethylformamide (DMF) were placed-in a 250 ml.round-bottom flask fitted with either a mechanical stirrer, refluxcondenser and sintered glass gas bubbler. Chlorine gas was metered intothe reaction mixture at a rate of 4 milliequivalents/min. and dilutedwith dry air entering at a rate of about 200-300 cc/min. The gases werethoroughly mixed in a large (2 liter) Erlenmeyer flask fitted with gasinlet tubes at the top and an exit tube at the bottom. The reactionmixture was initially two phase but became homogeneous as thehalogenation reaction proceeded. The reaction was begun at roomtemperature but the temperature slowly rose to about 50C. as thereaction proceeded. No attempt was made to cool the system. After thedesired amount of chlorine was introduced, the reaction was worked upimmediately.

Most of the DMF was distilled from the reaction at 40 to 50C under oilpump vacuum. The distillation was done directly from the reaction flask,which was suitably fitted with a distillation head. The receiver wasanother flask cooled in a dry ice-acetone bath and litted with acold-finger dry ice condenser. After most of the DMF was removed theproduct was dissolved in dichloromethane and this solution was extractedwith water. The layers were separated and the organic phase removed,dried (MgSO.,) and the solvent evaporated as described above. By leavingthe product at 40 C on a rotary evaporator under oil pump vacuumovernight, the DMF was removed leaving 15.1 g. (91 percent) of thechloroformoxylated soybean oil.

An equivalent amount of bromine is substituted for the chlorine in theabove process and the corresponding bromoformate derivative of soybeanoil is formed.

An equivalent amount of tallow oil, based on the-degree of unsaturation,is substituted for the soybeanoil in the above process and the processis done at 120C. The chloroformate derivative of tallow is formed.

An equivalent amount of dimethylcyclohexanamide is substituted for thedimethylformamide in the above process and the chlorocyclohexanatederivative of soybean oil is formed.

1n the above process there is substituted for the soybean oil anequivalent amount, based on the degreeof unsaturation, of palm oil,whale oil, babassu oil, tung oil, Neats-foot oil, coconut oil, oliveoil, lard and corn oil, respectively, and the formation of thecorresponding chloroformate of the respective oils results.

EXAMPLE 1V Reaction of Oleic Acid with Chlorine in Dimethylformamide Onegram mole of oleic acid, one gram mole of water and a ten-fold excess ofdimethylformamide are stirred at 120C. while a stream of chlorine gasadmixed equally with air is bubbled through the reaction mixture at arate of 24 grams of chlorine per hour for three hours. Work-up asdescribed above yields the chloroformyloxy derivatives of stearic acidisomeric at carbon atoms 9 and 10. The process is run at reactiontemperatures of 30C., 100C. and 200C., at 1,100 and 1,000 psi.,respectively, and the chloroformyloxy esters are formed in good yields.

EXAMPLE V Reaction of Oleic Acid with Chlorine in Dimethylalkanyl AmidesAccording to the procedure of Example 1, a mixture of one mole of oleicacid, one mole of chlorine, one mole of water and about a 15-fold volumeexcess of dimethylformamide (DMF) are reacted at 50C. The reactionproduct is a mixture of chloroformyloxy derivatives of stearic acid,isomeric at carbon atoms 9 .and 10.

In like manner, dimethylacetamide, dimethylpropionamide,dimethylbutyramide, dimethylpentanamide, dimethyldecanamide, anddimethylbenzamide, respectively, are substituted in equivalent volumefor the DMF in the above process and yield, respectively, thechloroacetate, chloropropionate, chlorobutyrate, chloropentanate,chlorodecanate, and chlorobenzoate derivatives of stearic acid, saidderivatives being isomeric at carbon atoms 9 and 10.

EXAMPLE Vl Reaction of Oleic Acid with Bromine in DimethylalkanoylAmides According to the procedure of Example I, a mixture of one mole ofoleic acid, one mole of bromine, one mole of water and about a l5-foldvolume excess of dimethylformamide (DMF) are reacted at 50C. Thereaction product is a mixture of bromoformyloxy derivatives of stearicacid, isomeric at carbon atoms 9 and 10.

The reaction is run at -l0C., 0C. and 50C. and the same results areobtained in that the respective bromoalkanoates of stearic acid areformed. The same results are obtained at l, 10 and 50 atmospherespressure.

REACTlON B EXAMPLE V11 Chlorination of l-Decene in DimethylformamideContaining More Than One Equivalent of Water A mixture of 6.3 g. (0.045mole) of l-decene, 8 g. (0.45 mole) of water and 100 ml. drydimethylformamide was placed in a 250 ml. flask equipped with amechanical stirrer. A mixture of chlorine and air was passed into thereaction mixture, which was maintained at 50C., at a rate of 4 meq.Cl,/min. After the theoretical amount of chlorine had been added themixture was stirred for 1 hour without heating. Extraction with etheryielded a colorless oil which was shown by gasliquid chromatography tobe composed of 85 percent OH Cl dichlorodecene. Distillation yielded6.95 g. percent yield) of the chlorohydrin, b.p. 6568/0.06 mm. Hg.

An equivalent amount of an olefin selected from the group consisting ofl-butene, l-pentene, l-hexene, 1- octene, l-dodecene,1-tetradecene,l-hexadecene, loctadecene, l-eicosene, 2-eicosene, 3-eicosene, 3-hexadecene, 2-decene, 2-dodecene, 2-heptene, 2-methyl-3-heptene,l-phenyl-2- dodecene, cyclohexene and cyclododecene is substituted forthe l-decene in the above process and the reaction is carried out at100C. and 150C. in an autoclave. Formation of the correspondingchlorohydrins isomeric at the original position of olefinic unsaturationresults.

Two moles of water, 1 mole of l-decene and 1.5 moles ofdimethylformamide are admixed and reacted with 1 mole of chlorine at200C. The two isomeric decane chlorohydrins are formed.

EXAMPLE V111 Bromination of l-Decene in Dimethylformamide ContainingMore Than One Equivalent of Water A mixture of 5 ml. (3.7 g., 0.026mole) of l-decene, 5 ml. of water, and 70 ml. of dimethylformamide wasrapidly stirred and 1.4 ml. (4.2 g., 0.026 mole) of bromine was addeddropwise at 30C. The yellow solution was stirred for one hour thenpoured into 300 ml. of water. Three-150 ml. diethyl ether extracts oftheaqueous mixture were combined and dried over MgSO After removing theether by distillation, the yellow oil was analyzed by gas-liquidchromatography and was shown to contain, by area percent, 20 percent1,2- dibromodecane, withthe remaining 80 percent consisting of the two1,2-bromohydrin isomers.

An equivalent amount of dimethylpropionamide or diethylacetamide issubstituted for the dimethylformamide in the above process and thereaction is run at C.; decane bromohydrin is formed.

EXAMPLE 1X Chlorination of Methyl Oleate in Dimethylformamide ContainingMore Than One Equivalent of Water Methyl oleate (4.5 g., 0.015 mole) and5 ml. H O were dissolved in 65 ml. of dimethylformamide. The mixture wasrapidly stirred and a chlorine-air mixture (as previously described) wasbubbled into the solution through a sintered glass gas bubbler at about30C. The chlorine addition rate was maintained at 4 meq./min. until0.015 moles had been added. The mixture was poured into 300 ml. of H 0and extracted with three 150 ml. portions of diethyl ether. The combinedether extracts were dried over MgSO fi1tered,.and the ether was removedby distillation. Gas-liquid and thin layer chromatography indicated twocomponents in approximately an 80/20 mixture. The larger component wasfound to be a mixture of two 9,IO-chloroformyloXyisomers of methylstearate, and the corresponding chlorohydrins, while the smallercomponent was the methyl stearate impurity in the starting material.Elemental analysis indicated that the major component was a 2:1 mixtureof the chlorohydrin and its formate ester.

An equivalent among of a member selected from the group consisting ofethyl oleate, butyl oleate, pentyl oleate, oleic acid, ricinoleic acid,and methyl ricinoleate is substituted for the methyl oleate of the aboveprocess, and results the formation of the corresponding chlorohydrinderivatives, isomeric at the original position of olefinic unsaturation.

EXAMPLE x Chlorination of trans-S-Decene in Dimethylformamide ContainingMore Than One Equivalent of Water A total of 5 ml. (3.7 g., 0.026 mole)of trans-5- decene was dissolved in ml. of dimethylformamide and 5 ml.of 11 0 was added. The mixture was chlorinated by means of anair-chlorine mixture passed through a sintered glass gas bubblerdirectly into the stirred solution at 30C. The chlorine addition ratewas maintained at approximately 4 meq./min. until percent of thetheoretical chlorine has been added. The mixture was poured into 300 ml.of H 0 and extracted with three-150 ml. portions of diethyl ether. Thecombined ether extracts were dried over MgSO, and the ether was removedby distillation. Gas-liquid chromatographic analysis of the clear, oilyresidue indicated the reaction product to be composed of 10 percent 5,6-dichlorodecane, 44 percent of the 5-chloro-6- formyloxydecane and 46percent of the 5-chloro-6- hydroxy decane. When the reaction mixture wasallowed to stir one hour after the chlorine had been added, theformation of 5-chloro-6-hydroxydecane was 95 percent complete.

The dimethylformamide is replaced by an equivalent .amount ofdimethylacetamide, dimethylpropionamide,

dimethylbutyramide, dimethylpentanamide, dimethylhexanamide,dimethyloctanamide, dimethyldecanamide, dimethylbenzamide, ordibenzylbenzamide and the reaction carried out at C. and psi. in aclosed vessel; 5-chloro-6-hydroxydecane is formed.

EXAMPLE XI Reaction of Oleic Acid with Bromine in DimethylalkanoylAmides Containing More Than One Equivalent of Water According to theprocedure of Examples VIII, one mole of oleic acid and one mole ofbromine are reacted in a mixture of two moles of water and five moles ofdimethylformamide, at a temperature of 200C. in an autoclave. Thecompounds 9-bromo-l0-hydroxystearic acid and 9-hydroxy-l0-bromostearicacid are secured.

Iodine is used in place of bromine and the reaction .is run at 50C. and180C. and the iodohydrin derivatives of stearic acid, isomeric at carbonatoms 9 and 10, are formed.

Chlorine is used in place of bromine and the reaction is run at 50C.,150C. and 200C. and the chlorohydrins of stearic acid, isomeric at'carbon atoms 9 and 10, are formed.

One pound of soybean oil containing about 40-60 percent by weight ofunsaturated triglyceride is treated together with 1 gallon of water andone gallon of dimethylformamide at 70C. by bubbling chlorine gas throughthe mixture until analysis (infrared) indicates saturation of theolefinic bond is complete. The reac-' tion product proves to be amixture of the chlorohydrins of soybean oil triglycerides.

Neats-foot oil, tallow, lard and corn oil are substituted in the abovereaction with substantially equivalent results in that the correspondinghalohydrins are thereby secured.

The dimethylformamide is replaced by a member selected from the groupconsisting of dimethylacetamide, dimethylpropionamide,dimethylbutyramide, dimethylpentanamide, dimethyldecanamide anddimethylbenzamide and equivalent results are obtained in that thehalohydrin derivatives of the olefins are formed.

REACTION C EXAMPLE XII Chlorination of l-Decene in DimethylformamideContaining More Than One Equivalent of Water Above 160C. The reactionmixtures of Example VII are prepared and the reactions are carried outat 200C. in an autoclave. The vicinal glycol derivatives of thecorresponding olefins are thereby secured.

EXAMPLE XIII Bromination of l-Decene in Dimethylformamide ContainingMore Than One Equivalent of Water Above 160C.

The reaction mixtures of Example VIII are prepared and the reactionsdone at 180C. and 100 psi. in an autoclave. The vincinal glycol,1,2-dihydroxydecane, is obtained.

EXAMPLE XIV Chlorination of Methyl Oleate in DimethylformamideContaining More Than One Equivalent of Water Above 160C.

The reaction mixtures of Example IX are prepared and the reactions arecarried out at 200C. and 200 psi. in an autoclave. The correspondingvicinal glycols of the respective alkyl and phenyl oleates are obtained.

EXAMPLE XV Chlorination of trans--Decene in Dimethylformamide ContainingMore Than One Equivalent of water Above 160C.

The reaction mixtures of Example X are prepared and the reactions arecarried out at 160C., 200C. and 250C. at autoclave pressures of and 100atmospheres; 5,6-dihydroxydecane is formed.

EXAMPLE XVI Reaction'of Oleic Acid With Bromine in DimethylakanoylAmides Containing More Than OneEquivalent of Water Above 160C.

To each of the reaction mixtures of Example XI is added an additionalone equivalent weight of water. The mixtures are heated at 160C. and thevicinal glycols (corresponding to the original olefins) are secured. Thereaction is done at 170C. and 50 psi. and at 300C. and 100 psi., in anautoclave, with the same results.

What is claimed is: Y

1. A process for preparing vincinal glycols from olefins, comprisinghalogenating said olefins in the presence of an amide of the formulaRC(O)NRR"', wherein R is a member selected from the group consisting ofhydrogen, normal, branch-chained and cyclic alkyl groups containing fromone to about 10 carbon atoms and phenyl and wherein R" and R' are eachmembers selected from the group consisting of normal, branch-chained andcyclic alkyl groups containing from about one to about 10 carbon atomsand phenyl, and at least three moles of water per mole of olefin, at atemperature above 160C.

2. A process according to claim 1 wherein the halogen is a memberselected from the group consisting of chlorine and bromine.

3. A process according to claim 1 wherein the olefin is an unsaturatedglyceride.

4. A process according to claim 1 wherein the olefin is a memberselected from the group consisting of loctene, l-decene, l-dodecene,l-tetradecene, l-

hexadecene, l-octadecene, oleic acid, methyl Oleate,-

ricinoleic acid, and methyl ricinoleate.

5. A process according to claim 1 wherein the amide is a member selectedfrom the group consisting of dimethylformamide, dimethylacetamide,dimethylpropionamide, dimethylbutyramide, diethylpentanamide,dimethyloctanamide, dimethylnonanamide, dimethyladecanamide, anddimethylbenzamide.

6. A process according to claim 1 where the halogen is chlorine, theolefinis a member selected from the group consisting of l-octene,l-decene, l-dodecene, l-tetradecene, l-hexadecene, l-octadecene, oleicacid, methyl oleate, ricinoleic acid, ricinolenic acid, lard, tallow,soybean oil, and methyl ricinoleate and wherein the amide is a memberselected from the group consisting of dimethylformamide,dimethylacetamide, dimethylpropionamide, dimethylbutyramide,dimethylpentanamide, dimethyloctanamide, dimethylnonamide,dimethyldecanamide and dimethylbenzamide.

7. A process according to claim 1 comprising reacting an olefin of theformula wherein each R is a member selected from the group consisting ofhydrogen, alkyl, aryl, carboxyalkyl, alkoxy, alkylglycerylester,alkylester, nitroalkyl, haloalkyl and polyalkoxyalkyl, with a halogenselected from the group consisting of chlorine and bromine in thepresence of an amide of the formula RIC(O)NRIIRIII wherein R is a memberselected from the group consisting of hydrogen, normal, branch-chainedand cyclic alkyl groups containing from about one to about 10 carbonatoms and phenyl, and R" and R' are each members selected from the groupconsisting of normal, branched-chain and cyclic alkyl groups containingfrom one to about 10 carbon atoms and phenyl, in the presence of atleast 3 moles of water per mole of olefin,

2. A process according to claim 1 wherein the halogen is a memberselected from the group consisting of chlorine and bromine.
 3. A processaccording to claim 1 wherein the olefin is an unsaturated glyceride. 4.A process according to claim 1 wherein the olefin is a member selectedfrom the group consisting of 1-octene, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene, oleic acid, methyl oleate,ricinoleic acid, and methyl ricinoleate.
 5. A process according to claim1 wherein the amide is a member selected from the group consisting ofdimethylformamide, dimethylacetamide, dimethylpropionamide,dimethylbutyramide, dimethylpentanamide, dimethyloctanamide,dimethylnonanamide, dimethyladecanamide, and dimethylbenzamide.
 6. Aprocess according to claim 1 where the halogen is chlorine, the olefinis a member selected from the group consisting of 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, oleic acid,methyl oleate, ricinoleic acid, lard, tallow, soybean oil, and methylricinoleate and wherein the amide is a member selected from the groupconsisting of dimethylformamide, dimethylacetamide,dimethylpropionamide, dimethylbutyramide, dimethylpentanamide,dimethyloctanamide, dimethylnonanamide, dimethyldecanamide anddimethylbenzamide.
 7. A process according to claim 1 comprising reactingan olefin of the formula